Process of manufacturing organic acids, esters and alcohols



Patented July 22, 1952 Q mS- The present invention hasfor'one of-itsobjects a process for manufacturing organic acids by' -the hydrolysis of their testers,- whi'ch" process constitutes an improvement: (ml-the process wherein soluble bases are used to'-'cataly'zelthe hydrolysis.

mote the respective -hydrolysis and al'coholysis rgacpions- Tl-ie reactionsi involved in the processes to 'which the present invention" is -applied may-be represented by the general equation:

R(|3 0R' ROH R-fi)OR" ROH where R and R represent organic radicals and R" represents hydrogen or an organic radical. Stated in broad terms, the present invention relates to an improvement in the process of reacting organic esters with an OH-containing compound of the group consisting of water and alcohols.

The substitution of a soluble base, i. e. the catalyst used by the prior art, by an anion exchanger of the present invention, presents great advantages. separation of the catalyst from the resultant product and facilitates the handling of the latter. Moreover, where the esterified acid is a strong acid, it combines in whole or in part, upon being set free, with the anion exchanger and the formed alcohol can thus be readily separated from the reaction medium by filtration and distillation at atmospheric pressure or by vacuum distillation, or by entrainment with steam before or after filtration, or by any other appropriate means. Moreover, the anion exchangers whose activity has become exhausted can be readily regenerated for further use by treatment with an alkali e. g. with dilute alkaline solutions. Further, the invention may also be carried out at atmospheric pressure. The use of autoclaves is therefore rendered unnecessary and a very simple apparatus can be used in carrying out the invention.

The process of the present invention is par- In particular, it enables the ready ..j2,604,482 i 1. I I RMAhUr cTUmNG ORGANIC. ,Es'rERs AND ALCOHOLS 1 peehineywompaghie de" P d ication April; 1 7, 1950, ,s'er

n France April 28;"1949,

(01. zen-410.9)

ticularlyvaluable for {the preparatio-n such as the "alkylesters of l higher fatt' the alcoholysis of glyceridescon fat 1.11. 1,.1; v Us In order to obtaingoodyields in all of these operations, it is advisable to use the Water or the alcohol'employed in; the reactioniii-"excess of stoichiometri'cproportions: f l I Asanion exch an:gers' for arry ng he present invention therecan be'used'amine-resins,

. such as furfuraldehyde-meta phnylene-diamine resins, formaldehyde-amino-{ethylene-urea: resins, polyamin'ostyrolene resins, 'etc and "especially those whose amino groupsfhave been rendered tertiary or c1uaternary by-a suitable treatment, for example" by' methylation by methyl-sulfate.

The following examples 'are givensolely 'by w'ay of illustrationof the invention, and-not-by' wa'y of limitation of either the esters treated, mesmporti'on's of the reagents or the-anio usetiv r To 100 grams of essence of sweet lavender containing 55% of linalol acetate (as determined by alkaline saponification) there are added 30 grams of an anion exchanger .in a basic state, such as meta-phenylene-diamine-formaldehyde resin or formaldehyde-amino-ethy1ene-urea resin, or their quaternary amino products, and the mixture is heated under reflux conditions with 250 cc. of Water for hour to 1 hour. The reaction mixture is thereupon subjected to entrainment with steam, yielding a distillate from which it is possible to isolate by intensive fractionation 39 grams of very pure linalol boiling at C. at 10 mm. pressure.

Example 2 Amyl salicylate is treated with excess of water in the presence of an anion'exchanger in the manner indicated in Example 1. The anion exchanger retains a portion of the salicylic acid formed by hydrolysis, this portion being the greater the higher the polarity of the anion exchanger; the remainder of the acid isseparated by decanting from the reaction mixture the aqueous liquor which contains, in addition to 7 hours.

all alkaline reaction disappears. The anion exchanger, thus regenerated, may be used in a new operation. The liquor decanted from the original reaction mixture-as indicated above-is now alkalized and steam distilled to recover the amyl alcohol. The alkalizedaqueous liquors from both operations described above are combined, concentrated and suitably treated with an acid to recover free salicylic acid.

Example 3 a a To 100 parts by weight of melted crude coconut butter, there are added 35 parts byweight I of an anion exchanger such as described in Example 1 and 400 to 600 (preferably, 500) parts by weight of absolute ethyl alcohol. The mixture is heated and refluxed for land /2 to 2 tillation, while the anion exchanger is separated from the residue of the distillation by decanting. the latter in a hot condition. The formed ethyl laurate can be recovered from the decanted residue by subjecting the residue to rectification under vacuum conditions.

Example 4 The operation is the same as in Example 3. except that the absolute ethyl alcohol is replaced by pure methyl alcohol boiling at 64 C. Methyl 'laurate is obtained as one of; the final products.

The excess alcohol is removed by dis! 4 3. A process according to claim 1 in which the spent anion exchange compound is regenerated for further use by treating it with an alkali compound.

4. A process according to claim 3 in which the anion exchange compound is regenerated with a dilute alkaline solution.

5. A process according to claim 1 in which the resins used as anion exchangers comprise the condensation product of aldehydes and amines. 64A process according to claim 5 in which the alkalinity of the anion exchanger used has beenenhanced' by transforming itsamino groups into tertiaryamines.

7. A processaccording to claim 5 in which the alkalinity. of the anion exchanger used has been enhanced by transforming its amino groups into quaternary amines.

'8. A process according to claim 1 in which alkyl esters of higher fatty acids are produced by alcoholysisof glycerides contained in natural fats. .L

9. A process according toclaim8 in which an alkyl laurate is produced'from crude coconut butter by alcoholysis with an aliphatical'cohol.

. l GEZA-AUS'IERWEIL- REFERENCES CITED The following references are of recordinthe file of'this patent:

. UNITED STATES PATENTS v Number Name ..Date 2,494,366 Sprules Jan'. 1 0,i'195 0 OTHER REFERENCES f Sussman: Ind. & Eng. Chem..38 (1946),", pa; 1228-30. V Winters et al.: Ind; and Engphems;

March 1, 1949, pages 460-4163. y 

1. THE IMPROVEMENT IN THE METHOD OF REACTING CARBOXYLIC ACID ESTERS WITH AN OH-CONTAINING COMPOUND OF THE GROUP CONSISTING OF WATER AND ALCOHOLS UNDER CONDITIONS EFFECTIVE TO SECURE HYDROLYSIS AND ALCOHOLYSIS RESPECTIVELY, WHICH CONSISTS IN CARRYING OUT THE REACTION IN THE PRESENCE OF AN INSOLUBLE ORGANIC BASIC ANION EXCHANGE COMPOUND. 